SORFERT PROCESS TRAINING

March 2011

Theoretical background
Chemical & Physical principles in the Urea process

• Contents:

• Chemical reactions
• Definitions
• Phase diagrams
• Liquid gas equilibrium
Liquid-
• 3 phase diagrams (Carbamate)
• Reaction kinetics & Pool condensation

March, 2011
Formation of Carbamate, condensation

3 2 4 2

Ammonium
carbamate

Exothermic reaction: Released condensation heat H = -28.5

28.5 kcal/mol
Fast !

March, 2011
Formation of Urea

Ammonium Urea
carbamate

Endothermic reaction: H = 3 to 6 kcal/mol

Slow !

March, 2011
Formation of biuret

Urea Bi ret
Biuret

Endothermic reaction
Slow !

March, 2011
Definitions

N/C ratio : The molar ratio of Ammonia and Carbon

dioxide in the initial mixture.

H/C ratio : The ratio between the number of moles of

water and the number of moles of carbon
dioxide in the initial mixture.

March, 2011
Calculations to determine process parameters

N/C molar ratio

Sample location: Liquid outlet reactor
Typical value: 3 00 mol/mol
3.00
Purpose: To control the synthesis at optimum
conditions

mUrea mNH3
2* 
N  MUrea M NH 3
C mUrea mCO2

MUrea M CO2

7
Calculations to determine process parameters

H/C molar ratio

Sample location: Liquid outlet reactor
Typical value: 0 41 mol/mol
0.41
Purpose: To determine the external water
(amount of water entering the
synthesis)
m H 2O mUrea

M H 2O M Urea
H 
C mUrea mCO2

M Urea M CO2

8
Definitions

CO2 efficiency: The ratio between the number of moles of

carbon dioxide that have contributed to the
conversion to urea and the total number of
moles of carbon dioxide in a reaction system.

NH3 efficiency: The ratio between the number of moles of

ammonia that have contributed to the
conversion to urea and the total number of
moles of ammonia in a reaction system
system.

March, 2011 Process Description

Calculations to determine process parameters

CO2 efficiency
Sample location: Liquid outlet reactor
Typical value: 60 %
Purpose: To determine the reaction efficiency

mUrea
M Urea
 CO  * 100 %
2
mUrea mCO2

M Urea M CO2

10
Calculations to determine process parameters

NH3 efficiency
Sample location: Liquid outlet Stripper
Typical value: 79
Purpose: To determine the stripping efficiency

mUrea
2*
M Urea
 NH  * 100 %
3
mUrea m NH 3
2* 
M Urea M NH 3

11
Sample result MW Actual mixture Starting mixture
((% by
y wt)) Kg/kmol (per 100 kg
(p g total)) (per 100 kg
(p g total))
Urea 34.6 % 60.056 0.57613 kmol 0 kmol
Biuret 0.1 % 103.081 9.7*10-4 kmol 0 kmol
CO2 17.5 % 44.01 0.39764 kmol 0.97571 kmol
NH3 30.1 % 17.031 1.76737 kmol 2.92254 kmol
H2O 17.7 % 18.016 0.98246 kmol 0.40439 kmol

N/C = 2.92254 / 0.97571 = 2.995 mol/mol (starting mixture !!)

H/C = 0.40439 / 0.97571 = 0.4145 mol/mol (starting mixture !!)
H2O/U
H2O/Urea = 0.98246
0 98246 / 0.57613
0 57613 = 1.705
1 705 mol/mol
l/ l (actual
( t l mixture
i t !!)
NH3/CO2 = 1.76737 / 0.39764 = 4.4446 mol/mol (actual mixture !!)

March, 2011
Warer

March, 2011
Ammonia

March, 2011
CO2

March, 2011
Carbamate

March, 2011
Refresher binary phase diagrams

Hexane-Octane
P= 1 bar
130

120

110
Temperatu re (C)

100

90

80

70

60
0 0.2 0.4 0.6 0.8 1
100% 100%
Hexane Molfraction Octane
Refresher binary phase diagrams

Hexane-Octane
T-X P= 1 bar
130
diagram
120

110
Boiling point of
Temperatu re (C)

100 Octane (126 C)

Boiling point of
Hexane (69 C)
90

80

70

60
0 0.2 0.4 0.6 0.8 1
100% 100%
Hexane Molfraction Octane
Refresher binary phase diagrams

Hexane-Octane
P= 1 bar
130

120 Gas

110
Temperatu re (C)

100
L+G
L G

90

80 Liq id
Liquid

70

60
0 0.2 0.4 0.6 0.8 1
100% 100%
Hexane Molfraction Octane
Refresher binary phase diagrams

Hexane-Octane
Boiling
Composition
Co pos t o
P= 1 bar
130
of first gas
G
bubble
120
((~10%
Octane))
Octane 110
Boiling point of
Temperatu re (C)

100 mixture ((82 C))

L+G
L G

90

80

L
70

60
0 0.2 0.4 0.6 0.8 1
100% 100%
Hexane Molfraction Octane
Refresher binary phase diagrams

Hexane-Octane
Boiling P= 1 bar
130
Gas G Liquid
(~20% Octane) 120
(~55% Octane)
110
Temperatu re (C)

L+G
100

90

80

Equilibrium! 70
L

60
0 0.2 0.4 0.6 0.8 1
100% 100%
Hexane Molfraction Octane
Refresher binary phase diagrams

Hexane-Octane
Condensatio P= 1 bar
Composition
p
n 130
of first liquid
G
drop
Initial dewpoint of 120
((~80%
mixture (104 C) Octane)
110
Temperatu re (C)

100

90 L+G

80

L
70

60
0 0.2 0.4 0.6 0.8 1
100% 100%
Hexane Molfraction Octane
Refresher binary phase diagrams

Hexane-Octane
Condensatio P= 1 bar
n 130
Gas G Liquid
(~20% Octane) 120
(~55% Octane)
110
Temperatu re (C)

L+G
100

90

80

Equilibrium! 70
L

60
0 0.2 0.4 0.6 0.8 1
100% 100%
Hexane Molfraction Octane
Refresher binary phase diagrams

T-X diagram P-X diagram

(P = constant) (T = constant)
H
Hexane-Octane
O t Hexane Octane
Hexane-Octane
P= 1 bar T= 100 C
130 3

120 G 2.5

110
L
2
Temp erature (C)

Pres sure (bar)

100
L+G 1.5
90 L+G
1
80
L G
0.5
70

60 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
100% 100% 100% 100%
Molfraction Hexane Molfraction Octane
Hexane Octane

P-X diagram looks like T-

T-X diagram
“Upside
p down”
Refresher binary phase diagrams

Chloroform-Acetone
P= 1 bar Boiling point of
65 Chloroform
64
(61.5 C)
63

62
Temperatture (C)

61
Boiling point of 60
Acetone
59
(56.3 C)
58

57

56
55
0 0.2 0.4 0.6 0.8 1
100%
mol. fraction 100%
Acetone
Chloroform
Refresher binary fase diagrams

Azeotrope:
65.5% Chloroform Chloroform-Acetone
(64.5 C) P= 1 bar Boiling point of
65 Chloroform
(61.5 C)
64
63
62
Tem peratture (C)

61
Boiling point of 60
Acetone 59 Boiling points
(56.3 C) of mixtures
58
57
56
55
0 0.2 0.4 0.6 0.8 1
100% 100%
mol. fraction
Acetone Chloroform
Refresher binary phase diagrams

Chloroform-Acetone Liquid + gas

65
64 Gas
Liquid + gas
63

62
Temperatture (C)

61

60
59
58
Liquid
57

56
55
0 0.2 0.4 0.6 0.8 1
100% 100%
mol. fraction
Acetone Chloroform
Refresher binary phase diagrams

Chloroform-AcetoneAzeotrope Liquid + gas

65
64 Gas
Liquid + gas
63

62
Temperatture (C)

61

60 Gas is rich in
59
Chloroform
Gas is rich in 58
acetone Liquid
57

56
55
0 0.2 0.4 0.6 0.8 1
100% 100%
mol. fraction
Acetone Chloroform
Refresher binary phase diagrams

(Positive) Azeotrope:
Maximum temperature at a given
pressure.

Or vice versa:
Minimum
Mi i pressure att a given
i
temperature.
System NH3-CO2 (simplified)

Azeotrope!
p Gas
P= constant
P

mperaturre (P > 90 bar)

L+G1

L
Tem

L+G2

CO2 NH3
System NH3-CO2-H2O (simplified)

H2O
CO2

NH3

March, 2011 Process Description

System NH3-CO2-H2O (simplified)

H2O
CO2

NH3

March, 2011 Process Description

System NH3-CO2-H2O (simplified)

H2O
CO2

NH3

March, 2011 Process Description

System NH3-CO2-H2O (simplified)

Gas top-ridge line

Liquid top-ridge
top ridge line

H2O
CO2

NH3

March, 2011 Process Description

System NH3-CO2-H2O (simplified)

Gas top-ridge line

Liquid top-ridge
top ridge line

H2O
CO2

NH3

March, 2011 Process Description

System NH3-CO2-H2O (simplified)

March, 2011 Process Description

System NH3-CO2-Urea-H2O

NH3

P= 130
bar

160ºC

170

180

Ch i l
Chemical
190

equilibrium
i b
isobar
CO2
Urea.1H2
O

March, 2011 Process Description

System NH3-CO2-Urea-H2O

Chemical equilibrium: Influence of temperature

N/C = 3.0
3 0 mol/mol
H/C = 0.0 mol/mol
System NH3-CO2-Urea-H2O

Chemical equilibrium: Influence of N/C ratio

T = 185 C
H/C = 0.0 mol/mol
System NH3-CO2-Urea-H2O

Chemical equilibrium: Influence of N/C ratio

T = 185 C
H/C = 0.0 mol/mol
System NH3-CO2-Urea-H2O

Chemical equilibrium: Influence of N/C ratio

CO2
Conversion
goes up Which is the best N/C
ratio to choose?

NH3
Conversion
goes down
System NH3-CO2-Urea-H2O

Chemical equilibrium: Influence of N/C ratio

CO2
Conversion
goes up
Maximize Urea
Concentration!
NH3
Conversion
goes down Azeotrope !
System NH3-CO2-Urea-H2O

NH3
Reaction
paths P= 130
P
bar
NH2COONH4
ammoniumcarbamate
N/C = 3 mol/mol
160ºC

170

180

190
“Ideal ?”

N/C = 2 mol/mol
CO2
Urea.1H2O
Optimum conditions for Synthesis operation

• High temperature
• Optimum N/C
/ ratio ((azeotropic point))
• Minimum amount of water
• Maximum system pressure (control inerts)

Psynthesis = Psystem + Pinert

March, 2011 Process Description

Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

100% A 60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

60 40 100% B
50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

60 40 100% C
50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80% A 80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

60% A 80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

40% A 80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

20% A 80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

0%A 80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

60 40

50 50
70 % B
40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

60 40

50 50
30 % B
40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

60 40

50 50
0%B
40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

60 40

50 50
60 % C
40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
90 10

80 20

70 30

60 40

50 50
20 % C
40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
10 % A
90 10

80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60

% of A
Ternary systems:  diagrams refresher

C
10 % A
90 10 20 % B
80 20

70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60

% of A
Ternary systems:  diagrams refresher

C
10 % A
90 10 20 % B
80 20 70 % C
70 30

60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60

% of A
Ternary systems:  diagrams refresher

C
10 % A
90 10
20 % B
80 20 70 % C
70 30
Total: 100%
60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60

% of A
Ternary systems:  diagrams refresher

C
1 2
90 10 Mixing: straight line

80 20

70 30

60 40
3
50
2 50

40 60

3
30 70

20 80

10 90
1
A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
1 2
90 10 Mixing: relative amounts
rule
80 20

70 30

60 40
3
50
2 50

40 60

3 Relative
Relative 30 70

amount of 2 amount of 1
20 80

10 90
1
A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

2 C Separation:
straight line
90 10

1 80 20

70 30

60 40

50
2 50

40 60

11
3 30 70

20 80

10 90
3
A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

2 C Separation:
straight line
90 10

1 80 20

70 30

60 40

50 50

3
40 60

11
3 30
2
70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

2 C Separation:
straight line
90 10

1 80 20

70 30

60 40

50 2 50

40 60

11
3 30 70

20 80

10 90

A 3 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

2 C Separation: relative
amount rule
90 10

1 80 20

70 30

60 40

50 2 50

40 60

11 Relative
3 30
amount of 3
70

20 80

10 90

A 3 50 40 30 20 10
B
90 80 70 60
Relative
amount of 2
Ternary systems:  diagrams refresher

C
Ratio’
90 10 s
80 20

70 30

Constant
60 40
ratio B:C
50 50
(1:2)
(1 2)
40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
Ratio’
90 10 s
Constant ratio 80 20

A/C 70 30

(20:80 = 1 : 4) 60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Ternary systems:  diagrams refresher

C
Ratio’
90 10 s
Two ratio’s 80 20

define a 70 30

composition 60 40

50 50

40 60

30 70

20 80

10 90

A 50 40 30 20 10
B
90 80 70 60
Cristalization point of Carbamate

April 23, 2010 Operations 71

Cristalization point of Carbamate

Analysis:
NH3 37.3 % wt
CO2 40.5 % wt
Water 22.2 % wt

April 23, 2010 Operations 72

Cristalization point of Carbamate

Analysis:
NH3 37.3 % wt
CO2 40.5 % wt
Water 22.2 % wt

April 23, 2010 Operations 73

Cristalization point of Carbamate

Analysis:
NH3 37.3 % wt
CO2 40.5 % wt
Water 22.2 % wt

April 23, 2010 Operations 74

Cristalization point of Carbamate

Analysis:
NH3 37.3 % wt
CO2 40.5 % wt
Water 22.2 % wt

Cristallization Temp.
Temp = 92° C

Tpr

T > T cryst

TCW

April 23, 2010 Operations 75

Reaction kinetics

equilibrium
95%


CO2

FA E
F.A.E

Residence Time
76
Pool condensation

Characteristics

• High heat transfer coefficient

(small heat exchanging area)
Wetted cooling surface
• Liquid
q residence time
• Pressure drop

Frequently employed in urea process

High pressure:
• HP scrubber
• Pool
P l condenser
d

Low pressure:
• Low pressure carbamate condenser
• Reflux condenser
• Flash tank condenser

77
Technological advantages pool condenser versus falling
film condenser

Pool condenser Falling

g film condenser

Heat/Mass transfer  High turbulance  Restricted by laminair

layer between gas and
liquid film
 Large transfer area  Restricted area
(bubbles) (tubes)

 Large LMTD d due

e to  Small LMTD
urea reaction Tprocess = 170°C
Tprocess = 175°C

78
Design of the pool condenser

• Process Design
- Shell side 140 bar synthesis pressure
175°C
- Tube
T b side
id 44.5
5 bar
b steam/BFW
/BFW
- Gas dividing system with flow deflector plates

• Mechanical Design
- Stainless steel
- U-tube bundle
- Internal bore welding
- Tube supports

79
Optimum reactor design

F.A.E. Equilibrium
(%)

60%

Condensing Reaction
part part t ((time))

80